Polymers with varied and useful properties may be produced in processes using at least two polymerization catalysts, at least one of which is a selected iron or cobalt catalyst, for the synthesis of polyolefins. Novel polymers with improved properties are made using a selected ethylene oligomerization catalyst to form xcex1-olefins and a polymerization catalyst capable of copolymerizing ethylene and xcex1-olefins.
Polyolefins are most often prepared by polymerization processes in which a transition metal containing catalyst system is used. Depending on the process conditions used and the catalyst system chosen, polymers, even those made from the same monomer(s) may have varying properties. Some of the properties which may change are molecular weight and molecular weight distribution, crystallinity, melting point, branching, and glass transition temperature. Except for molecular weight and molecular weight distribution, branching can affect all the other properties mentioned.
It is known that certain transition metal containing polymerization catalysts containing iron or cobalt, are especially useful in polymerizing ethylene and propylene, see for instance U.S. patent applications Ser. No. 08/991,372, filed Dec. 16, 1997, now U.S. Pat. No. 5,455,555 and Ser. No. 09/006,031, filed Jan. 12, 1998 now U.S. Pat. No. 6,150,482 (xe2x80x9cequivalentsxe2x80x9d of World Patent Applications 98/27124 and 98/30612). It is also known that blends of distinct polymers, that vary for instance in molecular weight, molecular weight distribution, crystallinity, and/or branching, may have advantageous properties compared to xe2x80x9csinglexe2x80x9d polymers. For instance it is known that polymers with broad or bimodal molecular weight distributions may often be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Also, thermoplastics such as crystalline polymers may often be toughened by blending with elastomeric polymers.
Therefore, methods of producing polymers which inherently produce polymer blends are useful especially if a later separate (and expensive) polymer mixing step can be avoided. However in such polymerizations one should be aware that two different catalysts may interfere with one another, or interact in such a way as to give a single polymer.
Various reports of xe2x80x9csimultaneousxe2x80x9d oligomerization and polymerization of ethylene to form (in most cases) branched polyethylenes have appeared in the literature, see for instance World Patent Application 90/15085, U.S. Pat. Nos. 5,753,785, 5,856,610, 5,686,542, 5,137,994, and 5,071,927, C. Denger, et al,. Makromol. Chem. Rapid Commun., vol. 12, p. 697-701 (1991), and E. A. Benham, et al., Polymer Engineering and Science, vol. 28, p. 1469-1472 (1988). None of these references specifically describes any of the processes herein or any of the branched homopolyethylenes claimed herein.
This invention concerns a polyethylene which has one or both of a structural index, ST, of about 1.4 or more, and a processability index, PR of about 40 or more, provided that if ST is less than about 1.4, said polymer has fewer than 20 methyl branches per 1000 methylene groups.
This invention also concerns a polyethylene which has at least 2 branches each of ethyl and n-hexyl or longer and at least one n-butyl per 1000 methylene groups, and has fewer than 20 methyl branches per 1000 methylene groups, and obeys the equation
[xcex7] less than 0.0007 Mw0.63
wherein [xcex7] is the intrinsic viscosity of said polyethylene in 1,2,4-trichlorbenzene at 150xc2x0 C. and Mw is the weight average molecular weight.